Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries

Today, lithium–ion batteries are the dominant technology on the market for powering portable electronic devices and due to their remarkable characteristics, such as high energy and power density, low self–discharge rate, no memory effect, and long service life, are the most promising candidate for a...

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Autor: Llusco Quispe, Aleksei Windsor
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2020
País:Chile
OAI Identifier:oai:repositorio.anid.cl:10533/249982
Acceso en línea:https://hdl.handle.net/10533/249982
Access Level:acceso abierto
Palabra clave:Ingeniería y Tecnología
Ingeniería de los Materiales
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dc.title.es_CL.fl_str_mv Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
Desarrollo de nanomateriales catódicos en base a LiMn2O4 con dopaje de Mg para baterías de ion litio de alta densidad de energía y potencia
title Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
spellingShingle Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
Llusco Quispe, Aleksei Windsor
Ingeniería y Tecnología
Ingeniería de los Materiales
Ingeniería de los Materiales
title_short Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
title_full Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
title_fullStr Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
title_full_unstemmed Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
title_sort Development of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteries
dc.creator.none.fl_str_mv Llusco Quispe, Aleksei Windsor
author Llusco Quispe, Aleksei Windsor
author_facet Llusco Quispe, Aleksei Windsor
author_role author
dc.contributor.advisor.none.fl_str_mv Grageda Zegarra, Mario Sandro
dc.contributor.institution.es_CL.fl_str_mv UNIVERSIDAD DE ANTOFAGASTA
dc.subject.oecd1n.es_CL.fl_str_mv Ingeniería y Tecnología
topic Ingeniería y Tecnología
Ingeniería de los Materiales
Ingeniería de los Materiales
dc.subject.oecd2n.es_CL.fl_str_mv Ingeniería de los Materiales
dc.subject.oecd3n.es_CL.fl_str_mv Ingeniería de los Materiales
description Today, lithium–ion batteries are the dominant technology on the market for powering portable electronic devices and due to their remarkable characteristics, such as high energy and power density, low self–discharge rate, no memory effect, and long service life, are the most promising candidate for applications in the transportation and electrical sectors. Among the cathodic materials based on insertion oxides, LiMn2O4 spinel (LMO) is one of the most promising candidates for large format lithium–ion batteries due to its various advantages such as easy preparation, low cost, abundance of raw materials, environmentally friendly, high cell voltage and high discharge rates. However, LMO presents severe capacity fading problems during cycling, especially when the temperature is above 55 °C. The reasons for the poor electrochemical performance of LMO are dissolution of Mn through dismutación of the Mn3+ ion and destructive Jahn–Teller structural distortion. In the present work, in order to overcome the disadvantages that decrease the cycling life of the LMO, a series of Li1+xMgyMn2-x-yO4 spinels (y = 0.00, 0.02, 0.05, 0.10) was optimized by Mg doping, nano-scale particle size reduction and an octahedral morphology. Octahedral nanoparticles of Li1+xMgyMn2-x-yO4 were synthesized by means of the Pechini–type sol–gel process assisted by ultrasound and purified Mg(OH)2 from residues generated in the production of Li2CO3 using natural brines from Salar de Atacama, located in the northern Chile, was used as a doping agent. The crystallization of a pure phase of cubic spinel of space group Fd-3m took place at 500 °C and a locally ordered spinel structure was obtained at a sintering temperature of 750 °C. The characterization of the physicochemical properties showed that Mg doping was an effective strategy to improve the structural rigidity of the spinels of Li1+xMgyMn2-x-yO4 with the reduction of the cell parameter, and suppress the amount of oxygen deficiencies. The optimal composition was identified for the spinel Li1.03Mn1.92Mg0.05O4 which showed an electrochemical performance superior to C/3 with a discharge capacity of 121.3 mAh g-1 and capacity retention of 94.0% after 100 cycles at room temperature. The high exchange current density and improved Li+ ion diffusion kinetics of Li1.03Mn1.92Mg0.05O4 resulted in high-rate capability and good cycling stability at high temperatures.
publishDate 2020
dc.date.issued.es_CL.fl_str_mv 2020
dc.date.accessioned.none.fl_str_mv 2021-07-22T15:20:55Z
2022-08-23T12:55:53Z
dc.date.available.none.fl_str_mv 2021-07-22T15:20:55Z
2022-08-23T12:55:53Z
dc.date.embargo.es_CL.fl_str_mv info:eu-repo/date/embargoEnd/2037-09-01
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spelling UNIVERSIDAD DE ANTOFAGASTALlusco Quispe, Aleksei Windsor2020https://hdl.handle.net/10533/249982http://purl.org/coar/access_right/c_abf2Ingeniería de los MaterialesIngeniería de los MaterialesIngeniería y TecnologíaDevelopment of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteriesGrageda Zegarra, Mario SandroUNIVERSIDAD DE ANTOFAGASTAChileLlusco Quispe, Aleksei Windsor2021-07-22T15:20:55Z2022-08-23T12:55:53Z2021-07-22T15:20:55Z2022-08-23T12:55:53Zinfo:eu-repo/date/embargoEnd/2037-09-012020Today, lithium–ion batteries are the dominant technology on the market for powering portable electronic devices and due to their remarkable characteristics, such as high energy and power density, low self–discharge rate, no memory effect, and long service life, are the most promising candidate for applications in the transportation and electrical sectors. Among the cathodic materials based on insertion oxides, LiMn2O4 spinel (LMO) is one of the most promising candidates for large format lithium–ion batteries due to its various advantages such as easy preparation, low cost, abundance of raw materials, environmentally friendly, high cell voltage and high discharge rates. However, LMO presents severe capacity fading problems during cycling, especially when the temperature is above 55 °C. The reasons for the poor electrochemical performance of LMO are dissolution of Mn through dismutación of the Mn3+ ion and destructive Jahn–Teller structural distortion. In the present work, in order to overcome the disadvantages that decrease the cycling life of the LMO, a series of Li1+xMgyMn2-x-yO4 spinels (y = 0.00, 0.02, 0.05, 0.10) was optimized by Mg doping, nano-scale particle size reduction and an octahedral morphology. Octahedral nanoparticles of Li1+xMgyMn2-x-yO4 were synthesized by means of the Pechini–type sol–gel process assisted by ultrasound and purified Mg(OH)2 from residues generated in the production of Li2CO3 using natural brines from Salar de Atacama, located in the northern Chile, was used as a doping agent. The crystallization of a pure phase of cubic spinel of space group Fd-3m took place at 500 °C and a locally ordered spinel structure was obtained at a sintering temperature of 750 °C. The characterization of the physicochemical properties showed that Mg doping was an effective strategy to improve the structural rigidity of the spinels of Li1+xMgyMn2-x-yO4 with the reduction of the cell parameter, and suppress the amount of oxygen deficiencies. The optimal composition was identified for the spinel Li1.03Mn1.92Mg0.05O4 which showed an electrochemical performance superior to C/3 with a discharge capacity of 121.3 mAh g-1 and capacity retention of 94.0% after 100 cycles at room temperature. The high exchange current density and improved Li+ ion diffusion kinetics of Li1.03Mn1.92Mg0.05O4 resulted in high-rate capability and good cycling stability at high temperatures.En la actualidad, las baterías de ion litio son la tecnología dominante del mercado para energizar dispositivos electrónicos portátiles y debido a sus notables características, tales como alta densidad de energía y potencia, baja velocidad de autodescarga, ausencia de efecto memoria y una larga vida útil, son el candidato más promisorio para aplicaciones en los sectores de transporte y eléctrico. Entre los materiales catódicos basados en óxidos de inserción, la espinela de LiMn2O4 (LMO) es uno de los candidatos más promisorios para baterías de ion litio de grandes formatos debido a sus varias ventajas tales como fácil preparación, bajo costo, abundancia de materias primas, compatible con el medio ambiente, alto voltaje de celda y altas velocidades de descarga. Sin embargo, el LMO presenta severos problemas de desvanecimiento de capacidad durante el ciclado, especialmente cuando la temperatura está por encima de 55°C. Las razones del pobre rendimiento electroquímico del LMO son la disolución del Mn a través de dismutación del ion Mn3+ y la nociva distorsión estructural de Jahn–Teller. En el presente trabajo, con el objetivo de superar las desventajas que disminuyen la vida de ciclado del LMO, una serie de espinelas de Li1+xMgyMn2-x-yO4 (y=0.00, 0.02, 0.05, 0.10) fue optimizada mediante el dopaje de Mg, reducción de tamaño de partícula a escala nanométrica y una morfología octaédrica. Las nanopartículas octaédricas de Li1+xMgyMn2-x-yO4 fueron sintetizadas mediante el proceso sol-gel tipo Pechini asistido por ultrasonido e Mg(OH)2 purificado de residuos generados en la producción de Li2CO3 utilizando salmueras naturales del Salar de Atacama, ubicado en el norte de Chile, fue utilizado como agente dopante. La cristalización de una fase pura de espinela cúbica de grupo espacial Fd-3m tuvo lugar a 500 °C y una estructura de espinela localmente ordenada fue obtenida a una temperatura de sinterizado de 750 °C. La caracterización de las propiedades fisicoquímicas evidenció que el dopaje con Mg fue una estrategia efectiva para mejorar la rigidez estructural de las espinelas de Li1+xMgyMn2-x-yO4 con la reducción del parámetro de celda, y suprimir la cantidad de deficiencias de oxígeno. La composición optima fue identificada para la espinela Li1.03Mn1.92Mg0.05O4 la cual mostró un rendimiento electroquímico superior a C/3 con una capacidad de descarga de 121.3 mAh g-1 y una retención de capacidad de 94.0 % después de 100 ciclos a temperatura ambiente. La alta densidad de corriente de intercambio y mejorada cinética de difusión del ion Li+ de Li1.03Mn1.92Mg0.05O4 resultó en altas velocidades de descarga y buena estabilidad del ciclado a altas temperaturas.Los materiales catódicos desarrollados en la tesis están protegidos por la patente WO201904105721151464https://hdl.handle.net/10533/249982instname: Conicytreponame: Repositorio Digital RI2.0info:eu-repo/grantAgreement//21151464info:eu-repo/semantics/dataset/hdl.handle.net/10533/93488Attribution-NonCommercial-NoDerivs 3.0 Chileinfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/3.0/cl/Ingeniería y TecnologíaIngeniería de los MaterialesIngeniería de los MaterialesDevelopment of cathodic nanomaterials based on LiMn2O4 with Mg doping for high energy and power density lithium-ion batteriesDesarrollo de nanomateriales catódicos en base a LiMn2O4 con dopaje de Mg para baterías de ion litio de alta densidad de energía y potenciainfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionTesisTesishttps://hdl.handle.net/10533/2499821bb28a52-ec68-4586-9ddf-70e5fd98bcd9virtual::60869-11bb28a52-ec68-4586-9ddf-70e5fd98bcd9virtual::60869-1THUMBNAILTesis doctorado - Aleksei Llusco - Universidad de Antofagasta.pdf.jpgIM Thumbnailimage/jpeg5194https://repositorio.anid.cl/bitstreams/8bde20d0-3fdc-46fc-965f-889b55a28706/downloadfb121b6dd3138a41db031ea57c22b8e8MD51TEXTTesis doctorado - Aleksei Llusco - Universidad de Antofagasta.pdf.txtExtracted texttext/plain498936https://repositorio.anid.cl/bitstreams/4ce47f31-272a-44cd-8483-b3c4b249b66a/downloadcb45d8c8f7925a5e50277e1ab45f59afMD52CC-LICENSElicense_rdfapplication/octet-stream1232https://repositorio.anid.cl/bitstreams/84be085d-4c77-41db-a7b7-156c360dbda7/downloadf97bcfdf58f3e17b5cec231112dab5b1MD53LICENSElicense.txttext/plain1779https://repositorio.anid.cl/bitstreams/93c7f55c-963d-4298-9982-1cf558c8a090/download593a6e7305c66c56041a9f9e15a649c1MD54ORIGINALTesis doctorado - Aleksei Llusco - Universidad de Antofagasta.pdfapplication/pdf21239161https://repositorio.anid.cl/bitstreams/fa6f9355-17fe-42ed-83de-83d870de3126/download26e50b3c2db286419acc1306e09e3369MD5510533/249982oai:repositorio.anid.cl:10533/2499822023-07-24 04:50:44.711http://creativecommons.org/licenses/by-nc-nd/3.0/cl/info:eu-repo/semantics/embargoedAccesshttps://repositorio.anid.clRepositorio ANIDaletelier@anid.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